Fluid Phase Equilibria 187–188 (2001) 61–70

Hydrate equilibrium data of 1,1,1,2-tetrafluoroethane

(HFC-134a), 1,1-dichloro-1-fluoroethane (HCFC-141b) and
1,1-difluoroethane (HFC-152a)
Deqing Liang a,b , Kaihua Guo b , Ruzhu Wang a , Shuanshi Fan b,∗
a
Institute of Refrigeration and Cryogenics, Shanghai Jiaotong University, P.O. Box A9802091, Shanghai 200030, PR China
b
Laboratory of Gas Hydrates and High-Pressure Fluids, Guangzhou Institute of
Energy Conversion, Guangzhou 510070, PR China
Received 16 November 2000; accepted 20 April 2001

Abstract
Liquid water–hydrate–vapor (Lw –H–V) and ice–hydrate–vapor (I–H–V) three phase equilibrium data of 1,1,1,2-
tetrafluoroethane (HFC-134a), 1,1-dichloro-1-fluoroethane (HCFC-141b) and 1,1-difluoroethane (HFC-152a) have
been reported in this paper. The data were measured in a sapphire cell with magnetic stirrer and data acquisition
system over a range of temperature (265.31–283.13, 268.41–281.49 and 264.72–288.15 K, respectively) and a range
of pressure (6–440, 6.2–40.2 and 49.5–443.7 kPa, respectively). Kihara potential parameters have been obtained
based on the experimental data. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Data; Hydrates; Refrigerants

1. Introduction

Gas hydrates are ice-like clathrates compounds, which are comprised of guest molecules (gas molecules)
and host molecules (water molecules), and form when some gases come into contact with water under
certain conditions of temperature and pressure, such as natural gas and some refrigerants. Now hydrate
structure has three main unit cells, namely structures — I, II and H [1–3]. In general, difference of the
structures of crystals of the hydrates is mainly caused by the guest molecule sizes.
Gas hydrates have been considered as one of the most promising phase change materials for cool storage
in air-conditioning systems. Cool storage system coupled to split system air conditioners can effectively
shift ∼95% of the electrical demand for residential cooling to off-peak periods [4]. Residential cool
storage systems based on ice, chilled water and eutectic hydrated salts have been built [5–9]. Due to the
low melting temperature and the heat transfer limitations for ice, very large storage volumes for chilled
∗
Corresponding author. Tel.: +86-20-87305777; fax: +86-20-87779767.
E-mail address: fanss@ms.giec.ac.cn (S. Fan).

0378-3812/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 1 2 ( 0 1 ) 0 0 5 2 6 - X
62 D. Liang et al. / Fluid Phase Equilibria 187–188 (2001) 61–70

water, and low heat transfer rates and volumetric storage density for eutectic hydrated salts, they are not
ideal cool storage media [10,11].
Refrigerant hydrates are promising for cool storage since they have proper melting temperature (4–7◦ C),
high volumetric storage density (about 302.4–464 kJ kg−1 ) and fair heat transfer coefficients [10,11]. For
practicing in cool storage systems connected with refrigerant gas hydrates, it is necessary to have reliable
equilibrium data of refrigerant gas hydrates.
Formation characteristics of some refrigerant gas hydrates have been studied [12–16]. However, less
information on their hydrate phase boundary especially for those of three phase ice–hydrate–vapor
(I–H–V) equilibrium, has yet been reported. In this study, a series of equilibrium tests containing three
phases of liquid water–hydrate–vapor (Lw –H–V) and I–H–V for 1,1,1,2-tetrafluoroethane (HFC-134a),
1,1-dichloro-1-fluoroethane (HCFC-141b) and 1,1-difluoroethane (HFC-152a) has been performed over
a range of temperature (265.31–283.13, 268.41–281.49 and 264.72–288.15 K, respectively) and a range
of pressure (6–440, 6.2–40.2 and 49.5–443.7 kPa, respectively). The hydrate dissociation data have been
used in optimization of the Kihara potential parameters in the hydrate equilibrium model, and a set of
Kihara potential parameters for these refrigerant hydrates was obtained.

2. Experimental

The experiments were carried out by using a high pressure PVT equipment for hydrates studies manu-
factured by ST company (France) in the present work. Fig. 1 is schematic diagram of the apparatus. The
apparatus consists of a cylindrical sapphire cell with a motorized piston. The maximum effective volume
of the cell is approximately 100 cm3 , and the minimum effective volume is 13.6 cm3 . The maximum
working pressure is 40 MPa. The sapphire cell is installed in an air bath, which has a working temperature
range of 253–393 K.
The cell contents are mixed by a stirrer and a circulating pump, and the stirrer is driven by a dc motor
located at the end of the piston and a magnetic coupling mounted outside the cell. The cell pressure is
measured using a COLE-PARMER (G-68000) absolute pressure transducer (0–0.9 MPa), and the cell
temperature is measured using platinum resistance thermometers. The cell volume can be adjusted by a
movable piston. The data of the cell temperature, pressure and volume are automatically recorded by a
personal computer.
The purity of HFC-134a, HCFC-141b and HFC-152a is 99.7, 99.5 and 99.5% used in this work,
respectively.
The test procedure was the same for all rigs. Before experiment, the cell was evacuated, then doubly
distilled water was charged in the cell, flushed with gases refrigerant and re-evacuated. Then, desired
amount of refrigerant was fed into the cell using sample syringe. The test fluids are confined in the cell
where its temperature is controlled within ±0.05 K, and the pressure of the cell is monitored by strain
gauge pressure transducer calibrated with an estimated accuracy of ±1%.
After water and sample have been charged in the cell, the temperature was then lowered to form hydrates.
For Lw –H–V three phase test, the temperature was then raised stepwise, at least 4 h for equilibrium to
be reached at each temperature, and the temperature and pressure were logged continuously and the
equilibrium data platted on a scatter-gram. The point at which the slope of P–T curve sharply changed
was considered as the hydrate dissociation point. This was also confirmed by visual observation. For
I–H–V three phase test, after the gas hydrate formed, then the temperature was cooled down to desired
 D. Liang et al. / Fluid Phase Equilibria 187–188 (2001) 61–70 63

Fig. 1. Schematic diagram of the experimental apparatus. DP: pressure transducer; RTD: temperature transducer.

temperature, when the temperature and pressure in the cell became constant with 12 h, the temperature and
pressure was taken as equilibrium data. The literature [12] carried out I–H–V three phase test using the
same method as that used in this work. The estimated accuracy of temperate and pressure measurements
in the above experiments is ±0.05 K and ±1%, respectively.
The HCFC-141b and HFC-134a can form structure-II hydrates, and fill big cavities in structure-II
hydrates, while HFC-152a can form structure-II hydrates or structure-I hydrates from its molecule size.
In general, HFC-152a forms structure-I hydrates.

3. Determination of Kihara potential parameters

The basic gas hydrate model was presented by van der Waals and Platteeuw [17]. The difference
between the chemical potential of water (µH
w ) in the hydrate phase and that in the hypothetical empty
64 D. Liang et al. / Fluid Phase Equilibria 187–188 (2001) 61–70
β
hydrate lattice (µw ) is expressed as
 


2

µβ−H
w = µβw − µH
w = −RT νm ln 1 − θjm  (1)
m=1 j =1

Cjm fj
θjm =  , j, k = 1, 2, . . . , N (2)
1 + k=1 Ckm fk
where R is the gas constant, T the absolute temperature, ν m the number of cavities of type m per water in
the unit cell, and fj the fugacity of the gas component j in the vapor phase, the original Peng–Robinson
equation [18] is used to calculate the fugacity of each refrigerant. When each phase is at equilibrium, it
is equal to that of the same component in any other coexisting phase. Cj m is the Langmuir constant and
applies to a j molecule in an m cavity, which depends on temperature and is determined by the relation:
 
4π R ω(r) 2
Cjm = exp − r dr (3)
kT 0 kT
where k is the Boltzmann’s constant and ω(r) the smoothed-cell potential function obtained using the
appropriate potential. Here r is the radial distance of the enclathrated gas molecule from the cavity center.
Following the suggestion of Mckoy and Sinanoglu [19], the Kihara potential with a spherical core is used.

 12  6 
σ∗ σ∗
U (r) = ∞, r ≤ 2α; U (r) = 4ε − , r > 2α (4)
r − 2α r − 2α

where U(r) is the potential energy of interaction between two molecules, α the core radius, σ = σ ∗ + 2α
the collision diameter and ε the depth of the energy well. The cell potential ω(r) is calculated by summation
of all gas–water interactions in the cell [19,20].
The chemical potential of the empty hydrate lattice is a function of temperature and pressure only and
it is given by the following equation [21]
β α/L  T (β−α)/L  P (β−α)/L
µw µw µ0w hw Vw
= + − dT + dP (5)
RT RT RT0 T0 RT2 0 RT
α/L
where µw is the chemical potential in the ice (α) or liquid (L) state depending on the temperature,
µ0w the chemical potential difference between the empty hydrate lattice and ice at the ice point and zero
(β−α)/L
pressure, P the equilibrium pressure and T0 the absolute temperature at ice point. Vw is molar
volume difference between an empty hydrate lattice and ice or liquid.
The molar enthalpy differences between an empty hydrate lattice and liquid water are functions of
temperature:
 T
(β−α)/L (β−α)/L
hw = hw +
0
CP w dT (6)
T0

where h0w is chemical potential difference between the empty hydrate lattice and ice at the ice point
(β−α)/L
and zero pressure, CP w is the heat capacity difference between the empty hydrate and ice or water.
 D. Liang et al. / Fluid Phase Equilibria 187–188 (2001) 61–70 65

Table 1
Reference properties of structure-I and structure-II hydrates [21]

Structure-I Structure-II

µ0w (J mol−1 ) 1120 931

h0w (J mol−1 )a 1714 1400
Vw (cm3 mol−1 )b 2.9959 3.39644
CP0 w (J mol−1 K−1 ) −34.583 −36.8607
T > T0 T > T0
−34.583 −36.8607
T < T0 T < T0
b (J mol−1 K2 )c 0.189 0.1809
T > T0 T > T0
0.0121 0.00377
T < T0 T < T0
a
In the liquid water region, subtract 6011 J mol−1 from h0w .
b
In the liquid water region, add 1.6 cm3 mol−1 to Vw .
c
Values to be used in CP w = CP0 w + b(T − T0 ).

Values of µ0w and h0w proposed by Holder et al. [21] were used. The heat capacity difference in Eq. (6)
is correlated using the expression provided by Holder et al. [21].
In process of generating optimum values of the Kihara potential parameters for gas–water interaction,
the classical mixing rules were used for calculation of the gas–water interaction and determined the
Kihara parameters, the mixing rules are as follows:
σg + σw
σ =
2
ε = (εg εw )1/2
α = 21 αg
where α w = 0 (see literature [19]), σ w = 342.6 pm and εw /k = 116.4 K [22].
Since the solubility in liquid water of refrigerants employed in this study is very low and the formation
pressures are also low, the effect of the solubility in water is negligible here.
Table 1 gives the reference properties of the hydrate structures used in this work. A set of Kihara
potential parameters of HFC-134a, HCFC-141b and HFC-152a are listed in Table 2. These parameters
were obtained by minimizing the absolute average deviation between the calculated and measured hydrate

Table 2
Kihara potential parameters for HFC-134a, HCFC-141b, and HFC-152aa

α (pm) σ ∗ (pm) ε/k (K)

HFC-134a 65.3 361.2 353.3

HCFC-141b 69.6 367.8 421.1
HFC-152a 60.0 300.6 466.0
a
σ ∗ = σ − 2α
66 D. Liang et al. / Fluid Phase Equilibria 187–188 (2001) 61–70

Table 3
Dissociation pressures for HFC-134a gas hydrate

T (K) P (kPa)

I–H–V 265.31 39.3

267.48 41.7
269.62 46.2
271.43 49.4
Lw –H–V 273.51 56.6
274.82 73.9
276.12 96.3
278.23 148.4
280.46 235.7
281.51 294.0
282.50 363.2
282.92 397.8
283.13 414.4

dissociation pressures. It is obvious that the Kihara potential parameters should be only used together
with the reference parameters presented in Table 1.

4. Experimental results and discussions

The experimental hydrate dissociation pressures for HFC-134a, HCFC-141b and HFC-152a are pre-
sented in Tables 3–5.
Fig. 2 shows the experimental and calculated hydrate dissociation pressures for HFC-134a. It can be
seen from Fig. 2 that the Q2 quadruple point of HFC-134a measured in this work match very well with the

Table 4
Dissociation pressures for HCFC-141b gas hydrate

T (K) P (kPa)

I–H–V 268.41 6.2

269.73 6.6
270.94 6.9
272.13 7.1
Lw –H–V 273.41 7.8
274.61 10.0
275.32 11.5
277.45 17.8
278.70 22.9
279.61 27.5
280.54 33.2
281.49 40.2
 D. Liang et al. / Fluid Phase Equilibria 187–188 (2001) 61–70 67

Table 5
Dissociation pressures for HFC-152a gas hydrate

T (K) P (kPa)

I–H–V 264.72 49.5

267.45 58.2
268.89 61.3
270.31 64.9
272.25 71.3
Lw –H–V 273.39 77.2
276.03 101.9
276.92 115.9
279.26 144.7
283.26 242.8
284.17 274.3
285.85 330.9
286.82 373.8
287.16 397.5
288.10 440.4
288.15 443.7

earlier literature value [12]. The agreement between experimental data and calculations using optimized
Kihara potential parameters is very good and the maximum error in calculating dissociation pressure
is 4.5%.
Fig. 3 shows the experimental and calculated hydrate dissociation pressures for HCFC-141b. It can
be seen from Fig. 3 that the data measured in this work match very well with the earlier literature data
[13]. The agreement between experimental data and calculations is good also, and the maximum error in
calculating dissociation pressure is 4.8%.

Fig. 2. Experimental and calculated hydrate dissociation pressures for HFC-134a using optimized Kihara potential parameters.
68 D. Liang et al. / Fluid Phase Equilibria 187–188 (2001) 61–70

Fig. 3. Experimental and calculated hydrate dissociation pressures for HCFC-141b using optimized Kihara potential parameters.

Fig. 4. Experimental and calculated hydrate dissociation pressures for HFC-152a using optimized Kihara potential parameters.

Table 6
Q1 and Q2 quadruple points for HFC-134a, HCFC-141b and HFC-152a hydrates

Q1 (I–Lw –H–V) Q2 (LR –Lw –H–V)

T (K) P (kPa) T (K) P (kPa)

HFC-134a 273.21 53.7 283.13 414.4

HCFC-141b 273.14 7.5 281.49 40.2
HFc-152a 273.16 73.9 288.15 443.7
 D. Liang et al. / Fluid Phase Equilibria 187–188 (2001) 61–70 69

Fig. 4 shows the experimental and calculated hydrate dissociation pressures for HFC-152a. Again the
agreement between experimental data and calculations is good, and the maximum error in calculating
dissociation pressure is 4.5%.
Table 6 gives the Q1 and Q2 quadruple points for HFC-134a, HCFC-141b and HFC-152a hydrates, Q1
point was obtained from the intersection of the I–H–V line with the Lw –H–V line.

5. Conclusion

HFC-134a, HCFC-141b and HFC-152a hydrate formation properties have been studies in this work.
Experimental hydrate dissociation pressures for these refrigerants have been measured and reported over
a range of temperature (265.31–283.13, 268.41–281.49 and 264.72–288.15 K, respectively) and a range
of pressure (6–440, 6.2–40.2 and 49.5–443.7 kPa, respectively).
Kihara potential parameters have been obtained for these refrigerant hydrates based on the experimental
data. The parameters will be useful in predicting hydrate dissociation pressures in an extended application
of these experimental data.

List of symbols
C Langmuir-type constant (M Pa−1 )
CP w heat capacity of water (J mol−1 K−1 )
f fugacity (MPa)
h enthalpy (J mol−1 )
k Boltzmann’s constant (J K−1 mol−1 )
P pressure (MPa)
Q1 lower quadruple point (I–Lw –H–V)
Q2 upper quadruple point (Lw –H–V–LR )
R universal gas constant (J mol−1 K−1 )
T absolute temperature (K)
U(r) Kihara potential function

Greek letters
α Kihara hard core radius (pm)
β index of an empty hydrate phase
 difference of the values of at thermodynamic property of two phases
ε Kihara potential parameter (J mol−1 )
µ chemical potential (J mol−1 )
ν number of cavity
θ fractional occupancy of a cavity
σ Kihara distance parameter (pm)
ω(r) spherically symmetrical cell potential

Superscripts
0 at the ice point and zero pressure
H hydrate phase
70 D. Liang et al. / Fluid Phase Equilibria 187–188 (2001) 61–70

L index of liquid phase

V vapor phase

Subscripts
g gas molecule
j, k component indices
m cavity index
R refrigerant
w indicates a water phase

Acknowledgements

This work is supported by National Natural Science Foundation of China (no. 59836230), the Major
Basic Research Program (G2000026306) and Guangdong Provincial Natural Science Foundation of China
(no. 990039).

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